US20100047586A1 - Modified ethylene-vinyl alcohol copolymer, gas barrier resin, and molded article of the same - Google Patents

Modified ethylene-vinyl alcohol copolymer, gas barrier resin, and molded article of the same Download PDF

Info

Publication number
US20100047586A1
US20100047586A1 US12/485,598 US48559809A US2010047586A1 US 20100047586 A1 US20100047586 A1 US 20100047586A1 US 48559809 A US48559809 A US 48559809A US 2010047586 A1 US2010047586 A1 US 2010047586A1
Authority
US
United States
Prior art keywords
gas barrier
resin
vinyl alcohol
set forth
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/485,598
Inventor
Naoyuki Morooka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yokohama Rubber Co Ltd
Original Assignee
Yokohama Rubber Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yokohama Rubber Co Ltd filed Critical Yokohama Rubber Co Ltd
Assigned to THE YOKOHAMA RUBBER CO., LTD. reassignment THE YOKOHAMA RUBBER CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MOROOKA, NAOYUKI
Publication of US20100047586A1 publication Critical patent/US20100047586A1/en
Priority to US13/733,366 priority Critical patent/US8969475B2/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0008—Compositions of the inner liner
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/02—Alkylation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C5/00—Inflatable pneumatic tyres or inner tubes
    • B60C5/12—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim
    • B60C5/14—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim with impervious liner or coating on the inner wall of the tyre
    • B60C2005/145—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim with impervious liner or coating on the inner wall of the tyre made of laminated layers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L2011/047—Hoses, i.e. flexible pipes made of rubber or flexible plastics with a diffusion barrier layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer

Definitions

  • the present invention relates to a modified ethylene-vinyl alcohol copolymer, more particularly relates to a gas barrier resin comprising the modified ethylene-vinyl alcohol copolymer and a molded article prepared from the same, particularly a pneumatic tire and a hose.
  • Ethylene-vinyl alcohol copolymers have superior gas barrier property, but have the defect that they are interior in bending fatigue resistance. To improve on this, there is known a method of modifying an ethylene-vinyl alcohol copolymer with an epoxy compound. See Japanese Unexamined Patent Publication No. 2003-231715.
  • the present invention addresses the matter of improving the drawback of an ethylene-vinyl alcohol copolymer, that is, the bending fatigue resistance, without reducing gas barrier property and heat resistance.
  • the present invention is a modified ethylene-vinyl alcohol copolymer comprising 20 to 50 percent by mole of a structural unit (1) expressed by the following formula (1):
  • n indicates an integer of 2 to 7
  • m indicates an integer of 10 to 20
  • R 1 indicates a C 1 to C 20 aliphatic hydrocarbon group or aliphatic hydrocarbon group substituted with a mercapto group, thioester group, sulfenamide, vinyl group, methacryloxy group, or acryloxy group.
  • the modified ethylene-vinyl alcohol copolymer is preferably prepared by melt blending an ethylene-vinyl alcohol copolymer with an alkyl polyether silane expressed by the following formula (4):
  • R 2 is a methyl group or ethyl group
  • R 1 , n, and m are the same as above.
  • the present invention is a gas barrier resin comprising the modified ethylene-vinyl alcohol copolymer.
  • the gas barrier resin preferably contains 100 parts by weight of the modified ethylene-vinyl alcohol copolymer and 5 to 120 parts by weight of a soft resin modified by an acid anhydride.
  • the present invention is a molded article comprising the gas barrier resin.
  • the present invention is a laminate comprising a layer of the gas barrier resin and a layer of a resin and/or elastomer other than the gas barrier resin.
  • the resin other than the gas barrier resin is preferably at least one resin selected from the group consisting of a polyolefin, polyamide, polyester, polystyrene, polyurethane, poly(vinylidene chloride), poly(vinyl chloride), polyacrylonitrile, and polycarbonate.
  • the elastomer other than the gas barrier resin is preferably selected from the group consisting of a diene-based elastomer, urethane-based elastomer, olefin-based elastomer, and styrene-based elastomer.
  • the present invention is a pneumatic tire comprising the gas barrier resin or the laminate as an air barrier layer.
  • the present invention is a hose comprising the gas barrier resin or the laminate as an air barrier layer.
  • the modified ethylene-vinyl alcohol copolymer of the present invention is superior in gas barrier property, heat resistance, and bending fatigue resistance. Because the modified ethylene-vinyl alcohol copolymer of the present invention is superior in gas barrier property, heat resistance, and bending fatigue resistance, it may be suitably used as a gas barrier resin and in molded articles, particularly pneumatic tires and hoses, requiring a gas barrier property.
  • the modified ethylene-vinyl alcohol copolymer of the present invention comprises a structural unit (1), a structural unit (2), and a structural unit (3).
  • the structural unit (1) is a so-called ethylene unit expressed by the following formula (1):
  • the structural unit (2) is a so-called vinyl alcohol unit expressed by the following formula (2):
  • the structural unit (3) is a structural unit, containing an alkyl polyether silyl group in the side chain, expressed by the following formula (3):
  • n indicates an integer of 2 to 7, preferably an integer of 4 to 6, more preferably 5
  • m indicates an integer of 10 to 20, preferably an integer of 11 to 18, more preferably an integer of 12 to 16
  • R 1 indicates an aliphatic hydrocarbon group having one to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 3 to 5 carbon atoms.
  • R 1 may contain a mercapto group, thioester group, sulfenamide, vinyl group, methacryloxy group, or acryloxy group.
  • R 1 is particularly preferably 3-mercaptopropyl.
  • the modified ethylene-vinyl alcohol copolymer comprises 20 to 50 percent by mole, preferably 30 to 45 percent by mole, more preferably 35 to 40 percent by mole of the structural unit (1). If the content of the structural unit (1) is too low, there is a tendency for the bending fatigue resistance to be insufficient, and if too high on the other hand, there is a tendency for gas barrier property to become insufficient.
  • the modified ethylene-vinyl alcohol copolymer comprises 0.01 to 1 percent by mole, preferably 0.03 to 0.5 percent by mole, more preferably 0.05 to 0.25 percent by mole of the structural unit (3). If the content of the structural unit (3) is too low, there is a tendency for the bending fatigue resistance to be insufficient, and if too high on the other hand, there is a tendency for gas barrier property to become insufficient.
  • the modified ethylene-vinyl alcohol copolymer preferably comprises 49.9 to 79 percent by mole of structural unit (2).
  • the modified ethylene-vinyl alcohol copolymer may comprise structural units other than structural unit (1), structural unit (2), and structural unit (3) within a scope that does not hamper the effect of the present invention. Note that, the content of each structural unit in the modified ethylene-vinyl alcohol copolymer may be measured by NMR.
  • the modified ethylene-vinyl alcohol copolymer is an ethylene-vinyl alcohol copolymer comprising the structural unit (1) and structural unit (2) modified by an alkyl polyether silane shown in formula (4):
  • R 2 indicates a methyl group or ethyl group
  • R 1 , n, and m are the same as above.
  • the modified ethylene-vinyl alcohol copolymer may be prepared by melt blending the ethylene-vinyl alcohol copolymer and the alkyl polyether silane shown in formula (4).
  • the alkyl polyether silane shown in formula (4) reacts by condensation with the OH groups of the ethylene-vinyl alcohol copolymer whereby the alcohol is removed and the structural unit (3) is formed.
  • the blend ratio of the ethylene-vinyl alcohol copolymer and the alkyl polyether silane shown in formula (4) is, based on 100 moles of the total of the structural unit (1) and structural unit (2) of the ethylene-vinyl alcohol copolymer, 0.01 to 1 mole of the alkyl polyether silane shown in formula (4).
  • the conditions for melt blending are not particularly limited so long as they are conditions in which the ethylene-vinyl alcohol copolymer and the alkyl polyether silane shown in formula (4) react to form the structural unit (3), but for example a twin screw extruder may be used for processing at 200 to 270° C. for 1 to 5 minutes.
  • a commercial product may be used for the alkyl polyether silane shown in formula (4) or one may be synthesized.
  • An example of a commercial product is the VP Si363 made by Evonik Degussa. Synthesis may be performed as follows. Inside a reaction container, a silane compound having a trialkoxysilyl group (for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryioxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxytriethoxysilane) is added, dodecylbenzenesulfonic acid or other acid catalyst is added, and further 2 equivalents by mole of a polyoxyethylene alkyl ether (for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene
  • the gas barrier resin of the present invention comprises the modified ethylene-vinyl alcohol copolymer.
  • the gas barrier resin of the present invention may be comprised of only the modified ethylene-vinyl alcohol copolymer, however, it may contain other substances within a scope that does not hamper the effect of the present invention.
  • the gas barrier resin of the present invention may be a mixture comprising, other than the modified ethylene-vinyl alcohol copolymer, an acid anhydride modified soft resin (hereinafter also referred to simply as a “modified soft resin”). That is, the gas barrier resin of the present invention may be a mixture of a modified ethylene-vinyl alcohol copolymer and modified soft resin. The inclusion of modified soft resin can further improve the bending fatigue resistance.
  • the amount of the modified soft resin blended is, preferably, 5 to 120 parts by weight based on 100 parts by weight of the modified ethylene-vinyl alcohol copolymer. If the amount of the modified soft resin is too low, the improvement effect on the bending fatigue resistance will be lower, and if on the other hand, the amount of the modified soft resin is too high, there is a tendency for gas barrier property to become insufficient.
  • the mixture of the modified ethylene-vinyl alcohol copolymer and the modified soft resin is preferably a melt blend of the modified ethylene-vinyl alcohol copolymer and the modified soft resin.
  • the modified ethylene-vinyl alcohol copolymer and modified soft resin may be melt blended at a temperature greater than their melting temperatures.
  • the melt blending conditions are not particularly limited, however, for example, a twin screw extruder is used for blending at 200 to 270° C. for 1 to 5 minutes.
  • the acid anhydride modified soft resin is a soft resin modified by an acid anhydride.
  • a “soft resin” means a resin having a Young's modulus of not more than 100 MPa at room temperature.
  • the soft resin include an olefin-based polymer, ethylene-based polymer, ethylene- ⁇ -olefin copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, and ethylene-propylene rubber.
  • the compatibility with the modified ethylene-vinyl alcohol copolymer can be improved.
  • the acid anhydride in the modified soft resin can be suitably selected to give an appropriate compatibility with the modified ethylene-vinyl alcohol copolymer, however, preferably, the amount of the acid anhydride is 0.1 to 2 percent by weight based on the weight of the modified soft resin.
  • the acid anhydride modified soft resin includes an anhydrous maleate-modified ethylene- ⁇ -olefin copolymer.
  • it is an anhydrous maleate-modified ethylene-propylene copolymer or ethylene-butene copolymer.
  • These are commercially available and can be obtained as Tafmer® MP-0620 (anhydrous maleate-modified ethylene-propylene copolymer) and Tafmer® MP-7020 (anhydrous maleate-modified ethylene-butene copolymer) from Mitsui Chemicals, Inc.
  • the gas barrier resin of the present invention may comprise other substances within a scope of not hampering the effect of the present invention.
  • the gas barrier resin may be a mixture with a resin other than the modified soft resin such as poly(vinyl alcohol), ethylene-vinyl alcohol copolymer, polyamide, polyester, polyolefin, polystyrene, polyurethane resin, poly(vinylidene chloride), poly(vinyl chloride), polycarbonate, etc.
  • additives blended into it may comprise additives blended into it in addition to the above ingredients such as carbon black, silica, and other fillers, vulcanizing or cross-linking agents, vulcanizing or cross-linking accelerators, various types of oils, anti-aging agents, and other various types of additives generally blended in for resin use and other rubber composition use.
  • additives may be kneaded in by a general method to obtain a composition to be vulcanized or cross-linked.
  • the amounts of these additives blended may be made the conventional general amounts so long as not running counter to the object of the present invention.
  • the gas barrier resin of the present invention may be used as various gas barrier materials.
  • the gas barrier resin of the present invention may be used for various molded articles.
  • the shape of the molded article includes, but not limited to, a film shape, cylinder shape, etc.
  • the shaping method is not particularly limited and common methods may be used.
  • the gas barrier resin of the present invention can be made into a film using a T-die extruder, an inflation machine, etc., and the film may be suitably used as the inner liner of a pneumatic tire because of its superior gas barrier property, heat resistance, and bending fatigue resistance. Further, cylinder-shaped ones may be suitably used as hoses.
  • gas barrier resin of the present invention (hereinafter also simply referred to as a “gas barrier resin”) can be laminated to a resin other than the gas barrier resin of the present invention (hereinafter also simply referred to as “another resin”) or an elastomer other than the gas barrier resin of the present invention (hereinafter also simply referred to as an “elastomer”) to form a laminate.
  • another resin a resin other than the gas barrier resin of the present invention
  • elastomer an elastomer other than the gas barrier resin of the present invention
  • a laminate comprising a gas barrier resin layer and another resin and/or elastomer layer means either a two-layer laminate comprising a gas barrier resin layer and another resin layer, a two-layer laminate comprising a gas barrier resin layer and an elastomer layer, a three-layer laminate comprising a gas barrier resin layer, another resin layer, and an elastomer layer, a multi-layer laminate comprising one or more gas barrier resin layers and one or more other resin layers, a multi-layer laminate comprising one or more gas barrier resin layers and one or more elastomer layers, or a multi-layer laminate comprising one or more gas barrier resin layers, one or more other resin layers, and one or more elastomer layers.
  • the other resins include a polyolefin, polyamide, polyester, polystyrene, polyurethane, polyvinylidene chloride, polyvinyl chloride, polyacrylonitrile, and polycarbonate.
  • a polyolefin polyamide, polyester, polystyrene, polyurethane, polyvinylidene chloride, polyvinyl chloride, polyacrylonitrile, and polycarbonate.
  • One among these may be used alone, or a mixture of two or more may be used.
  • the elastomer includes a diene-based elastomer, urethane-based elastomer, olefin-based elastomer, and styrene-based elastomer. One among these may be used alone, or a mixture of two or more may be used. Further, the other resin and elastomer may be blended together and used.
  • layers (films) of each may be prepared and bonded with each other or a laminate may be prepared by coextrusion, however the latter is preferable.
  • coextrusion commonly used methods may be used. For example, coextrusion inflation and coextrusion blowing may be used.
  • a laminate comprising a layer of the gas barrier resin and a layer of another resin and/or an elastomer of the present invention may be used in various applications requiring a gas barrier property.
  • pneumatic tires or hoses may be prepared using these laminates as air barrier layers.
  • a commonly used method may be used. For example, when arranging an inner liner at an inner side of a carcass layer, the laminate of the present invention is placed on a tire forming drum in a cylindrical shape, a carcass layer, belt layer, tread layer, and other members made of unvulcanized rubber used in normal tire production are overlaid in that order, then the drum is pulled out to obtain a green tire. Next, this green tire is vulcanized in accordance with normal methods to produce the desired pneumatic tire.
  • a hose may be prepared as follows. First, pellets of the gas barrier resin of the present invention are used to extrude a thermoplastic elastomer composition on a mandrel coated with a release agent in advance from a resin extruder by the cross-head extrusion method to thereby form an inner tube. Further, another gas barrier resin of the present invention or a general thermoplastic elastomer may be extruded on top of the inner tube to form an inner tube outer layer. Next, when necessary, an adhesive is applied on the inner tube by coating or spraying.
  • a braiding machine is used to braid a reinforcing yarn or reinforcing steel wire on top of the inner tube.
  • an adhesive is coated on top of the reinforcing layer for bonding with the outer tube, then a resin is extruded from a cross-head resin extruder in the same way as the gas barrier resin of the present invention or the other generally used thermoplastic elastomer composition to form an outer tube.
  • the mandrel is removed, whereby a hose can be obtained.
  • the adhesive coated on the inner tube or the reinforcing layer includes an isocyanate-based, urethane-based, phenol resin-based, resorcin-based, chlorinated rubber-based, and HRH-based adhesives, however isocyanate-based and urethane-based adhesives are particularly preferable.
  • ethylene-vinyl alcohol copolymer As the ethylene-vinyl alcohol copolymer, EVAL-H171B having 38 percent by mole of structural unit (1) made by Kuraray Co., Ltd. was used, while as the alkyl polyether silane, three types of alkyl polyether silane of formula (5) were used:
  • Comparative Example 1 is an unmodified ethylene-vinyl alcohol copolymer and Comparative Examples 2 and 3 are modified ethylene-vinyl alcohol copolymers prepared using 2 percent by mole and 4 percent by mole, respectively, of glycidol in place of alkyl polyether silane.
  • Each modified ethylene-vinyl alcohol copolymer was continuously discharged from the extruder as strands, cooled with water, cut by a cutter into pellets, then shaped into a film by a T-die extruder (220° C.) to obtain a film having a thickness of 25 ⁇ m.
  • the temperature dependency of the specific heat was measured by heat analysis (DTA or DSC), and the peak temperature was recorded as the melting temperature.
  • anhydrous maleate-modified EPM (Tafmer® MP-0620 made by Mitsui Chemicals, Inc.) were added to 100 parts by weight of the modified ethylene-vinyl alcohol copolymer of Example 3 and melt kneaded to prepare a gas barrier resin.
  • the resin had a bending fatigue number of 52000, melting temperature of 160° C., and air permeability coefficient of 32.
  • Example 7 Other than the use of an unmodified ethylene-vinyl alcohol copolymer (EVAL-H171B made by Kuraray Co., Ltd. having an ethylene unit content of 38 percent by mole) in Example 7 in place of the modified ethylene-vinyl alcohol copolymer of Example 3, the gas barrier resin was prepared in the same manner as in Example 7. Upon evaluation, the resin had a bending fatigue number of 340, melting temperature of 161° C., and air permeability coefficient of 34.
  • EVAL-H171B unmodified ethylene-vinyl alcohol copolymer made by Kuraray Co., Ltd. having an ethylene unit content of 38 percent by mole
  • Example 7 From the evaluation results of Example 7 and Comparative Example 4, it is clear that using a modified ethylene-vinyl alcohol copolymer will result in a significant increase in bending fatigue resistance in comparison to the unmodified ethylene-vinyl alcohol copolymer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

Ethylene-vinyl alcohol copolymers have superior gas barrier properties, but are inferior in bending fatigue resistance. The present invention improves bending fatigue resistance without reducing the gas barrier property and heat resistance. An ethylene-vinyl alcohol copolymer having an ethylene content of 20 to 50 percent by mole is modified by incorporating 0.01 to 1% mol of a structural unit expressed by the following formula (3):
Figure US20100047586A1-20100225-C00001
wherein, n indicates an integer of 2 to 5, m indicates an integer of 10 to 20, and R1 indicates a C1 to C20 aliphatic hydrocarbon group provided that R1 may contain a mercapto group, thioester group, sulfenamide, vinyl group, methacryloxy group, or acryloxy group. The modified ethylene vinyl alcohol copolymer may be used as a gas barrier resin and this gas barrier resin may be shaped or laminated and used in various applications such as in pneumatic tires and hoses.

Description

    TECHNICAL FIELD
  • The present invention relates to a modified ethylene-vinyl alcohol copolymer, more particularly relates to a gas barrier resin comprising the modified ethylene-vinyl alcohol copolymer and a molded article prepared from the same, particularly a pneumatic tire and a hose.
    • BACKGROUND ART
  • Ethylene-vinyl alcohol copolymers have superior gas barrier property, but have the defect that they are interior in bending fatigue resistance. To improve on this, there is known a method of modifying an ethylene-vinyl alcohol copolymer with an epoxy compound. See Japanese Unexamined Patent Publication No. 2003-231715.
    • SUMMARY OF INVENTION
  • Technical Problem
  • However, if modifying an ethylene-vinyl alcohol copolymer with an epoxy compound, the bending fatigue resistance will be improved, but the gas barrier property and heat resistance (melting point) will tend to drop. The present invention addresses the matter of improving the drawback of an ethylene-vinyl alcohol copolymer, that is, the bending fatigue resistance, without reducing gas barrier property and heat resistance.
  • Solution to Problem
  • The present invention is a modified ethylene-vinyl alcohol copolymer comprising 20 to 50 percent by mole of a structural unit (1) expressed by the following formula (1):

  • —CH2—CH2—  (1)
  • a structural unit (2) expressed by the following formula (2):
  • Figure US20100047586A1-20100225-C00002
  • and 0.01 to 1 percent by mole of a structural unit (3) expressed by the following formula (3):
  • Figure US20100047586A1-20100225-C00003
  • wherein n indicates an integer of 2 to 7, m indicates an integer of 10 to 20, and R1 indicates a C1 to C20 aliphatic hydrocarbon group or aliphatic hydrocarbon group substituted with a mercapto group, thioester group, sulfenamide, vinyl group, methacryloxy group, or acryloxy group.
  • The modified ethylene-vinyl alcohol copolymer is preferably prepared by melt blending an ethylene-vinyl alcohol copolymer with an alkyl polyether silane expressed by the following formula (4):
  • Figure US20100047586A1-20100225-C00004
  • wherein R2 is a methyl group or ethyl group, and R1, n, and m are the same as above.
  • The present invention, further, is a gas barrier resin comprising the modified ethylene-vinyl alcohol copolymer.
  • The gas barrier resin preferably contains 100 parts by weight of the modified ethylene-vinyl alcohol copolymer and 5 to 120 parts by weight of a soft resin modified by an acid anhydride.
  • The present invention, further, is a molded article comprising the gas barrier resin.
  • The present invention, further, is a laminate comprising a layer of the gas barrier resin and a layer of a resin and/or elastomer other than the gas barrier resin.
  • The resin other than the gas barrier resin is preferably at least one resin selected from the group consisting of a polyolefin, polyamide, polyester, polystyrene, polyurethane, poly(vinylidene chloride), poly(vinyl chloride), polyacrylonitrile, and polycarbonate.
  • The elastomer other than the gas barrier resin is preferably selected from the group consisting of a diene-based elastomer, urethane-based elastomer, olefin-based elastomer, and styrene-based elastomer.
  • The present invention is a pneumatic tire comprising the gas barrier resin or the laminate as an air barrier layer.
  • The present invention, further, is a hose comprising the gas barrier resin or the laminate as an air barrier layer.
    • ADVANTAGEOUS EFFECTS OF INVENTION
  • The modified ethylene-vinyl alcohol copolymer of the present invention is superior in gas barrier property, heat resistance, and bending fatigue resistance. Because the modified ethylene-vinyl alcohol copolymer of the present invention is superior in gas barrier property, heat resistance, and bending fatigue resistance, it may be suitably used as a gas barrier resin and in molded articles, particularly pneumatic tires and hoses, requiring a gas barrier property.
    • DESCRIPTION OF EMBODIMENTS
  • The modified ethylene-vinyl alcohol copolymer of the present invention comprises a structural unit (1), a structural unit (2), and a structural unit (3).
  • The structural unit (1) is a so-called ethylene unit expressed by the following formula (1):

  • —CH2—CH2—  (1)
  • The structural unit (2) is a so-called vinyl alcohol unit expressed by the following formula (2):
  • Figure US20100047586A1-20100225-C00005
  • The structural unit (3) is a structural unit, containing an alkyl polyether silyl group in the side chain, expressed by the following formula (3):
  • Figure US20100047586A1-20100225-C00006
  • where n indicates an integer of 2 to 7, preferably an integer of 4 to 6, more preferably 5, m indicates an integer of 10 to 20, preferably an integer of 11 to 18, more preferably an integer of 12 to 16, and R1 indicates an aliphatic hydrocarbon group having one to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. However, R1 may contain a mercapto group, thioester group, sulfenamide, vinyl group, methacryloxy group, or acryloxy group. R1 is particularly preferably 3-mercaptopropyl.
  • The modified ethylene-vinyl alcohol copolymer comprises 20 to 50 percent by mole, preferably 30 to 45 percent by mole, more preferably 35 to 40 percent by mole of the structural unit (1). If the content of the structural unit (1) is too low, there is a tendency for the bending fatigue resistance to be insufficient, and if too high on the other hand, there is a tendency for gas barrier property to become insufficient.
  • The modified ethylene-vinyl alcohol copolymer comprises 0.01 to 1 percent by mole, preferably 0.03 to 0.5 percent by mole, more preferably 0.05 to 0.25 percent by mole of the structural unit (3). If the content of the structural unit (3) is too low, there is a tendency for the bending fatigue resistance to be insufficient, and if too high on the other hand, there is a tendency for gas barrier property to become insufficient.
  • Other than the structural unit (1) and structural unit (3) of the structural units composing the modified ethylene-vinyl alcohol copolymer, there is preferably the structural unit (2). That is, the modified ethylene-vinyl alcohol copolymer preferably comprises 49.9 to 79 percent by mole of structural unit (2). However, the modified ethylene-vinyl alcohol copolymer may comprise structural units other than structural unit (1), structural unit (2), and structural unit (3) within a scope that does not hamper the effect of the present invention. Note that, the content of each structural unit in the modified ethylene-vinyl alcohol copolymer may be measured by NMR.
  • The modified ethylene-vinyl alcohol copolymer is an ethylene-vinyl alcohol copolymer comprising the structural unit (1) and structural unit (2) modified by an alkyl polyether silane shown in formula (4):
  • Figure US20100047586A1-20100225-C00007
  • wherein R2 indicates a methyl group or ethyl group, and R1, n, and m are the same as above.
  • The modified ethylene-vinyl alcohol copolymer may be prepared by melt blending the ethylene-vinyl alcohol copolymer and the alkyl polyether silane shown in formula (4). By blending an ethylene-vinyl alcohol copolymer comprising 20 to 50 percent by mole of the structural unit (1) and the alkyl polyether silane shown in formula (4) at a temperature greater than their melting temperatures, the alkyl polyether silane shown in formula (4) reacts by condensation with the OH groups of the ethylene-vinyl alcohol copolymer whereby the alcohol is removed and the structural unit (3) is formed. The blend ratio of the ethylene-vinyl alcohol copolymer and the alkyl polyether silane shown in formula (4) is, based on 100 moles of the total of the structural unit (1) and structural unit (2) of the ethylene-vinyl alcohol copolymer, 0.01 to 1 mole of the alkyl polyether silane shown in formula (4). The conditions for melt blending are not particularly limited so long as they are conditions in which the ethylene-vinyl alcohol copolymer and the alkyl polyether silane shown in formula (4) react to form the structural unit (3), but for example a twin screw extruder may be used for processing at 200 to 270° C. for 1 to 5 minutes.
  • A commercial product may be used for the alkyl polyether silane shown in formula (4) or one may be synthesized. An example of a commercial product is the VP Si363 made by Evonik Degussa. Synthesis may be performed as follows. Inside a reaction container, a silane compound having a trialkoxysilyl group (for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryioxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxytriethoxysilane) is added, dodecylbenzenesulfonic acid or other acid catalyst is added, and further 2 equivalents by mole of a polyoxyethylene alkyl ether (for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, etc.) based on one equivalent by mole of the silane compound is added, and the mixture is reacted while being agitated at 10 to 100° C. temperature, preferably 20 to 60° C. temperature, for several hours under reduced pressure conditions, whereby an alkyl polyether silane is obtained.
  • The gas barrier resin of the present invention comprises the modified ethylene-vinyl alcohol copolymer. The gas barrier resin of the present invention may be comprised of only the modified ethylene-vinyl alcohol copolymer, however, it may contain other substances within a scope that does not hamper the effect of the present invention. For example, the gas barrier resin of the present invention may be a mixture comprising, other than the modified ethylene-vinyl alcohol copolymer, an acid anhydride modified soft resin (hereinafter also referred to simply as a “modified soft resin”). That is, the gas barrier resin of the present invention may be a mixture of a modified ethylene-vinyl alcohol copolymer and modified soft resin. The inclusion of modified soft resin can further improve the bending fatigue resistance. The amount of the modified soft resin blended is, preferably, 5 to 120 parts by weight based on 100 parts by weight of the modified ethylene-vinyl alcohol copolymer. If the amount of the modified soft resin is too low, the improvement effect on the bending fatigue resistance will be lower, and if on the other hand, the amount of the modified soft resin is too high, there is a tendency for gas barrier property to become insufficient.
  • The mixture of the modified ethylene-vinyl alcohol copolymer and the modified soft resin is preferably a melt blend of the modified ethylene-vinyl alcohol copolymer and the modified soft resin. The modified ethylene-vinyl alcohol copolymer and modified soft resin may be melt blended at a temperature greater than their melting temperatures. The melt blending conditions are not particularly limited, however, for example, a twin screw extruder is used for blending at 200 to 270° C. for 1 to 5 minutes.
  • The acid anhydride modified soft resin is a soft resin modified by an acid anhydride. A “soft resin” means a resin having a Young's modulus of not more than 100 MPa at room temperature. Examples of the soft resin include an olefin-based polymer, ethylene-based polymer, ethylene-α-olefin copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, and ethylene-propylene rubber.
  • By modifying the soft resin with an acid anhydride, the compatibility with the modified ethylene-vinyl alcohol copolymer can be improved. The acid anhydride in the modified soft resin can be suitably selected to give an appropriate compatibility with the modified ethylene-vinyl alcohol copolymer, however, preferably, the amount of the acid anhydride is 0.1 to 2 percent by weight based on the weight of the modified soft resin.
  • The acid anhydride modified soft resin includes an anhydrous maleate-modified ethylene-α-olefin copolymer. Preferably, it is an anhydrous maleate-modified ethylene-propylene copolymer or ethylene-butene copolymer. These are commercially available and can be obtained as Tafmer® MP-0620 (anhydrous maleate-modified ethylene-propylene copolymer) and Tafmer® MP-7020 (anhydrous maleate-modified ethylene-butene copolymer) from Mitsui Chemicals, Inc.
  • The gas barrier resin of the present invention, as mentioned above, may comprise other substances within a scope of not hampering the effect of the present invention. The gas barrier resin may be a mixture with a resin other than the modified soft resin such as poly(vinyl alcohol), ethylene-vinyl alcohol copolymer, polyamide, polyester, polyolefin, polystyrene, polyurethane resin, poly(vinylidene chloride), poly(vinyl chloride), polycarbonate, etc. Further, it may comprise additives blended into it in addition to the above ingredients such as carbon black, silica, and other fillers, vulcanizing or cross-linking agents, vulcanizing or cross-linking accelerators, various types of oils, anti-aging agents, and other various types of additives generally blended in for resin use and other rubber composition use. These additives may be kneaded in by a general method to obtain a composition to be vulcanized or cross-linked. The amounts of these additives blended may be made the conventional general amounts so long as not running counter to the object of the present invention.
  • The gas barrier resin of the present invention may be used as various gas barrier materials.
  • The gas barrier resin of the present invention may be used for various molded articles. The shape of the molded article includes, but not limited to, a film shape, cylinder shape, etc. The shaping method is not particularly limited and common methods may be used. The gas barrier resin of the present invention can be made into a film using a T-die extruder, an inflation machine, etc., and the film may be suitably used as the inner liner of a pneumatic tire because of its superior gas barrier property, heat resistance, and bending fatigue resistance. Further, cylinder-shaped ones may be suitably used as hoses.
  • The gas barrier resin of the present invention (hereinafter also simply referred to as a “gas barrier resin”) can be laminated to a resin other than the gas barrier resin of the present invention (hereinafter also simply referred to as “another resin”) or an elastomer other than the gas barrier resin of the present invention (hereinafter also simply referred to as an “elastomer”) to form a laminate. A laminate comprising a gas barrier resin layer and another resin and/or elastomer layer means either a two-layer laminate comprising a gas barrier resin layer and another resin layer, a two-layer laminate comprising a gas barrier resin layer and an elastomer layer, a three-layer laminate comprising a gas barrier resin layer, another resin layer, and an elastomer layer, a multi-layer laminate comprising one or more gas barrier resin layers and one or more other resin layers, a multi-layer laminate comprising one or more gas barrier resin layers and one or more elastomer layers, or a multi-layer laminate comprising one or more gas barrier resin layers, one or more other resin layers, and one or more elastomer layers.
  • The other resins include a polyolefin, polyamide, polyester, polystyrene, polyurethane, polyvinylidene chloride, polyvinyl chloride, polyacrylonitrile, and polycarbonate. One among these may be used alone, or a mixture of two or more may be used.
  • The elastomer includes a diene-based elastomer, urethane-based elastomer, olefin-based elastomer, and styrene-based elastomer. One among these may be used alone, or a mixture of two or more may be used. Further, the other resin and elastomer may be blended together and used.
  • As a method of production of the laminate, layers (films) of each may be prepared and bonded with each other or a laminate may be prepared by coextrusion, however the latter is preferable. For the coextrusion, commonly used methods may be used. For example, coextrusion inflation and coextrusion blowing may be used.
  • A laminate comprising a layer of the gas barrier resin and a layer of another resin and/or an elastomer of the present invention may be used in various applications requiring a gas barrier property. For example, pneumatic tires or hoses may be prepared using these laminates as air barrier layers.
  • As a method for producing a pneumatic tire using the laminate of the present invention as an air barrier layer, a commonly used method may be used. For example, when arranging an inner liner at an inner side of a carcass layer, the laminate of the present invention is placed on a tire forming drum in a cylindrical shape, a carcass layer, belt layer, tread layer, and other members made of unvulcanized rubber used in normal tire production are overlaid in that order, then the drum is pulled out to obtain a green tire. Next, this green tire is vulcanized in accordance with normal methods to produce the desired pneumatic tire.
  • As a method for producing a hose using the gas barrier resin of the present invention, a commonly used method may be used. For example, a hose may be prepared as follows. First, pellets of the gas barrier resin of the present invention are used to extrude a thermoplastic elastomer composition on a mandrel coated with a release agent in advance from a resin extruder by the cross-head extrusion method to thereby form an inner tube. Further, another gas barrier resin of the present invention or a general thermoplastic elastomer may be extruded on top of the inner tube to form an inner tube outer layer. Next, when necessary, an adhesive is applied on the inner tube by coating or spraying. Further, a braiding machine is used to braid a reinforcing yarn or reinforcing steel wire on top of the inner tube. When necessary, an adhesive is coated on top of the reinforcing layer for bonding with the outer tube, then a resin is extruded from a cross-head resin extruder in the same way as the gas barrier resin of the present invention or the other generally used thermoplastic elastomer composition to form an outer tube. Finally, the mandrel is removed, whereby a hose can be obtained. The adhesive coated on the inner tube or the reinforcing layer includes an isocyanate-based, urethane-based, phenol resin-based, resorcin-based, chlorinated rubber-based, and HRH-based adhesives, however isocyanate-based and urethane-based adhesives are particularly preferable.
    • EXAMPLES Examples 1 to 6 and Comparative Examples 1 to 3
  • To prepare a modified ethylene-vinyl alcohol copolymer, as the ethylene-vinyl alcohol copolymer, EVAL-H171B having 38 percent by mole of structural unit (1) made by Kuraray Co., Ltd. was used, while as the alkyl polyether silane, three types of alkyl polyether silane of formula (5) were used:
  • Figure US20100047586A1-20100225-C00008
  • wherein n=5 and m=12 (hereinafter referred to as “alkyl polyether silane 1”), n=5 and m=16 (hereinafter referred to as “alkyl polyether silane 2”), and n=5 and m=18 (hereinafter referred to as “alkyl polyether silane 3”).
  • The ethylene-vinyl alcohol copolymer and the alkyl polyether silane of the type and amount according to Table 1 were charged into a twin screw kneader (TEX44 made by Japan Steel Works) and melt kneaded at 230° C. for 3 minutes to obtain the modified ethylene-vinyl alcohol copolymer (Examples 1 to 6). Note that, Comparative Example 1 is an unmodified ethylene-vinyl alcohol copolymer and Comparative Examples 2 and 3 are modified ethylene-vinyl alcohol copolymers prepared using 2 percent by mole and 4 percent by mole, respectively, of glycidol in place of alkyl polyether silane.
  • Each modified ethylene-vinyl alcohol copolymer was continuously discharged from the extruder as strands, cooled with water, cut by a cutter into pellets, then shaped into a film by a T-die extruder (220° C.) to obtain a film having a thickness of 25 μm.
  • The following test methods were used to test the modified ethylene-vinyl alcohol copolymers.
  • [Bending Fatigue]
  • 50 sheets of the single layer films produced according to the above and cut into sizes of 21 cm by 30 cm were produced and, based on ASTM F 392-74, were bent 50 times, 100 times, 200 times, 250 times, 1000 times, 10000 times, 20000 times, 50000 times, 75000 times, and 100000 times, then measured for the number of pinholes using a Gelbo Flex Tester made by Rigaku Kogyo. At each number of bending times, measurement was performed five times and the average of these measurements was recorded as the number of pinholes. The measurement results were plotted with the number of bending times (P) as the abscissa and the number of pinholes (N) as the ordinate. The number of bending times to one pinhole was determined by extrapolation to 2 significant figures.
  • [Melting Temperature]
  • The temperature dependency of the specific heat was measured by heat analysis (DTA or DSC), and the peak temperature was recorded as the melting temperature.
  • [Air Permeability Coefficient]
  • Based on JIS K6404, samples were prepared and air permeability was measured at 60° C. The results were shown as values indexed to the value of the air permeability coefficient of Comparative Example 1 as 100. The greater the value, the more superior the gas barrier property.
  • The obtained test results are shown in Table 1. It is clear that the bending fatigue resistance of the alkyl polyether silane-modified ethylene-vinyl alcohol copolymers (Examples 1 to 6) of the present invention increases significantly in comparison to the unmodified ethylene-vinyl alcohol copolymer (Comparative Example 1). Further, the bending fatigue resistance of the epoxy modified ethylene-vinyl alcohol copolymers of the prior art (Comparative Examples 2 and 3) is improved, but the heat resistance and gas barrier property drop, while the bending fatigue resistance of the alkyl polyether silane-modified ethylene-vinyl alcohol copolymers (Examples 1 to 6) of the present invention can be improved without reducing heat resistance and gas barrier property.
  • TABLE 1
    Comp. Comp. Comp.
    Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 2 Ex. 3
    Alkyl polyether 0.05 mol % 0.08 mol % 0.10 mol % 0.25 mol %
    silane 1
    (n = 5, m = 12)
    Alkyl polyether 0.10 mol %
    silane 2
    (n = 5, m = 16)
    Alkyl polyether 0.10 mol %
    silane 3
    (n = 5, m = 18)
    Glycidol 2 mol % 4 mol %
    Bending fatigue 12 229 240 320 310 250 260 240 300
    number
    Melting 161 160 160 160 160 160 160 151 145
    temperature (° C.)
    Air permeability 100  95  94  94  96  98  96  85  75
    • Example 7
  • 80 parts by weight of anhydrous maleate-modified EPM (Tafmer® MP-0620 made by Mitsui Chemicals, Inc.) were added to 100 parts by weight of the modified ethylene-vinyl alcohol copolymer of Example 3 and melt kneaded to prepare a gas barrier resin. Upon evaluation, the resin had a bending fatigue number of 52000, melting temperature of 160° C., and air permeability coefficient of 32.
    • Comparative Example 4
  • Other than the use of an unmodified ethylene-vinyl alcohol copolymer (EVAL-H171B made by Kuraray Co., Ltd. having an ethylene unit content of 38 percent by mole) in Example 7 in place of the modified ethylene-vinyl alcohol copolymer of Example 3, the gas barrier resin was prepared in the same manner as in Example 7. Upon evaluation, the resin had a bending fatigue number of 340, melting temperature of 161° C., and air permeability coefficient of 34.
  • From the evaluation results of Example 7 and Comparative Example 4, it is clear that using a modified ethylene-vinyl alcohol copolymer will result in a significant increase in bending fatigue resistance in comparison to the unmodified ethylene-vinyl alcohol copolymer.

Claims (20)

1. A modified ethylene-vinyl alcohol copolymer comprising 20 to 50 percent by mole of a structural unit (1) expressed by the following formula (1):

—CH2—CH2—  (1)
a structural unit (2) expressed by the following formula (2):
Figure US20100047586A1-20100225-C00009
and 0.01 to 1 percent by mole of a structural unit (3) expressed by the following formula (3):
Figure US20100047586A1-20100225-C00010
wherein n indicates an integer of 2 to 7, m indicates an integer of 10 to 20, and R1 indicates a C1 to C20 aliphatic hydrocarbon group or aliphatic hydrocarbon group substituted with a mercapto group, thioester group, sulfonamide, vinyl group, methacryloxy group, or acryloxy group.
2. A modified ethylene-vinyl alcohol copolymer as set forth in claim 1, wherein the modified ethylene-vinyl alcohol copolymer is prepared by melt blending an ethylene-vinyl alcohol copolymer with an alkyl polyether silane expressed by the following formula (4):
Figure US20100047586A1-20100225-C00011
wherein R2 is a methyl group or ethyl group, and R1, n, and m are the same as the above.
3. A gas barrier resin comprising a modified ethylene-vinyl alcohol copolymer as set forth in claim 1.
4. A gas barrier resin as set forth in claim 3, comprising 100 parts by weight of the modified ethylene-vinyl alcohol copolymer and 5 to 120 parts by weight of a soft resin modified by an acid anhydride.
5. A molded article comprising a gas barrier resin as set forth in claim 3.
6. A laminate comprising a layer of a gas barrier resin as set forth in claim 3 and a layer of a resin and/or an elastomer other than the gas barrier resin.
7. A laminate as set forth in claim 6, wherein the resin other than the gas barrier resin is at least one resin selected from the group consisting of a polyolefin, polyamide, polyester, polystyrene, polyurethane, poly(vinylidene chloride), poly(vinyl chloride), polyacrylonitrile, and polycarbonate.
8. A laminate as set forth in claim 6, wherein the elastomer other than the gas barrier resin is selected from the group consisting of a diene-based elastomer, urethane-based elastomer, olefin-based elastomer, and styrene-based elastomer.
9. A pneumatic tire comprising a gas barrier resin as set forth in claim 3 as an air barrier layer.
10. A hose comprising a gas barrier resin as set forth in claim 3 as an air barrier layer.
11. A pneumatic tire comprising a laminate as set forth in claim 6 as an air barrier layer.
12. A hose comprising a laminate as set forth in claim 6 as an air barrier layer.
13. A gas barrier resin comprising a modified ethylene-vinyl alcohol copolymer as set forth in claim 2.
14. A molded article comprising a gas barrier resin as set forth in claim 4.
15. A laminate comprising a layer of a gas barrier resin as set forth in claim 4 and a layer of a resin and/or an elastomer other than the gas barrier resin.
16. A laminate as set forth in claim 15, wherein the resin other than the gas barrier resin is at least one resin selected from the group consisting of a polyolefin, polyamide, polyester, polystyrene, polyurethane, poly(vinylidene chloride), poly(vinyl chloride), polyacrylonitrile, and polycarbonate.
17. A laminate as set forth in claim 16, wherein the elastomer other than the gas barrier resin is selected from the group consisting of a diene-based elastomer, urethane-based elastomer, olefin-based elastomer, and styrene-based elastomer.
18. A laminate as set forth in claim 7, wherein the elastomer other than the gas barrier resin is selected from the group consisting of a diene-based elastomer, urethane-based elastomer, olefin-based elastomer, and styrene-based elastomer.
19. A gas barrier resin as set forth in claim 13, comprising 100 parts by weight of the modified ethylene-vinyl alcohol copolymer and 5 to 120 parts by weight of a soft resin modified by an acid anhydride.
20. A pneumatic tire comprising a gas barrier resin as set forth in claim 4 as an air barrier layer.
US12/485,598 2008-08-25 2009-06-16 Modified ethylene-vinyl alcohol copolymer, gas barrier resin, and molded article of the same Abandoned US20100047586A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/733,366 US8969475B2 (en) 2008-08-25 2013-01-03 Method for preparing a modified ethylene-vinyl alcohol copolymer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-215517 2008-08-25
JP2008215517A JP4488097B2 (en) 2008-08-25 2008-08-25 Gas barrier resin molded product or laminate

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/733,366 Division US8969475B2 (en) 2008-08-25 2013-01-03 Method for preparing a modified ethylene-vinyl alcohol copolymer

Publications (1)

Publication Number Publication Date
US20100047586A1 true US20100047586A1 (en) 2010-02-25

Family

ID=40941490

Family Applications (2)

Application Number Title Priority Date Filing Date
US12/485,598 Abandoned US20100047586A1 (en) 2008-08-25 2009-06-16 Modified ethylene-vinyl alcohol copolymer, gas barrier resin, and molded article of the same
US13/733,366 Expired - Fee Related US8969475B2 (en) 2008-08-25 2013-01-03 Method for preparing a modified ethylene-vinyl alcohol copolymer

Family Applications After (1)

Application Number Title Priority Date Filing Date
US13/733,366 Expired - Fee Related US8969475B2 (en) 2008-08-25 2013-01-03 Method for preparing a modified ethylene-vinyl alcohol copolymer

Country Status (6)

Country Link
US (2) US20100047586A1 (en)
EP (1) EP2159234B1 (en)
JP (1) JP4488097B2 (en)
KR (1) KR20100024343A (en)
CN (1) CN101659724B (en)
AT (1) ATE521644T1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130123428A1 (en) * 2008-08-25 2013-05-16 The Yokohama Rubber Col, Ltd. Method for Preparing a Modified Ethylene-Vinyl Alcohol Copolymer
US20150165586A1 (en) * 2013-12-17 2015-06-18 Fujibo Holdings, Inc. Resin Lapping Plate and Lapping Method Using the Same
US20160039247A1 (en) * 2013-03-15 2016-02-11 Bridgestone Americas Tire Operations, Llc Light-Weight Inner Tube And Related Methods
US20220186858A1 (en) * 2019-03-11 2022-06-16 Contitech Techno-Chemie Gmbh Coolant hose

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5440249B2 (en) * 2010-02-25 2014-03-12 横浜ゴム株式会社 Modified ethylene-vinyl alcohol copolymer, process for producing the same, and gas barrier resin composition
US9868267B2 (en) * 2011-05-31 2018-01-16 Bridgestone Corporation Multilayer structure, inner liner for pneumatic tire, and pneumatic tire
JP5911731B2 (en) * 2012-02-14 2016-04-27 株式会社ブリヂストン tire
RU2582521C2 (en) 2012-02-14 2016-04-27 Бриджстоун Корпорейшн Tyre
JP6021442B2 (en) * 2012-05-28 2016-11-09 横浜ゴム株式会社 Pneumatic tire

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4650721A (en) * 1983-12-23 1987-03-17 Mobil Oil Corporation Polypropylene barrier film and method of forming same
US5369168A (en) * 1992-08-03 1994-11-29 Air Products And Chemicals, Inc. Reactive melt extrusion grafting of thermoplastic polyvinyl alcohol/polyolefin blends
US20030130535A1 (en) * 2001-08-06 2003-07-10 Degussa Ag, Organosilicon compounds
US20040096683A1 (en) * 2001-05-14 2004-05-20 Kaoru Ikeda Modified ethylene-vinyl alcohol copolymer and method for the production thereof
US20040170787A1 (en) * 1999-07-29 2004-09-02 Kuraray Co. Ltd. Fuel container
US20060128870A1 (en) * 2004-12-10 2006-06-15 Marx Ryan E Filled polymer composites
US20070203274A1 (en) * 2006-02-24 2007-08-30 Karsten Korth Rubber mixtures
WO2007123220A1 (en) * 2006-04-18 2007-11-01 The Yokohama Rubber Co., Ltd. Layered low-permeability rubber product and pneumatic tire comprising the same
WO2008009514A1 (en) * 2006-07-17 2008-01-24 Evonik Degussa Gmbh Mixtures of silicon-containing coupling reagents
US20080314490A1 (en) * 2006-03-03 2008-12-25 The Yokohama Rubber Co., Ltd. Low Permeability Rubber Laminate and Pneumatic Tire Using the Same
US7662784B2 (en) * 1997-05-13 2010-02-16 Ipsen Pharma, S.A.S. Method for decreasing body weight using a somatostatin receptor agonist

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1076593A (en) * 1996-09-03 1998-03-24 Daicel Chem Ind Ltd Barrier composite film and its manufacture
JP2000071396A (en) * 1998-05-26 2000-03-07 Nakato Kenkyusho:Kk Gas barrier laminated film and its production
JP3851218B2 (en) 2001-05-14 2006-11-29 株式会社クラレ Gas barrier material comprising a modified ethylene-vinyl alcohol copolymer
JP2006167919A (en) * 2004-12-10 2006-06-29 Bridgestone Corp Laminate, its manufacturing method and tire using the laminate
JP4488097B2 (en) * 2008-08-25 2010-06-23 横浜ゴム株式会社 Gas barrier resin molded product or laminate

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4650721A (en) * 1983-12-23 1987-03-17 Mobil Oil Corporation Polypropylene barrier film and method of forming same
US5369168A (en) * 1992-08-03 1994-11-29 Air Products And Chemicals, Inc. Reactive melt extrusion grafting of thermoplastic polyvinyl alcohol/polyolefin blends
US7662784B2 (en) * 1997-05-13 2010-02-16 Ipsen Pharma, S.A.S. Method for decreasing body weight using a somatostatin receptor agonist
US20040170787A1 (en) * 1999-07-29 2004-09-02 Kuraray Co. Ltd. Fuel container
US20040096683A1 (en) * 2001-05-14 2004-05-20 Kaoru Ikeda Modified ethylene-vinyl alcohol copolymer and method for the production thereof
US20030130535A1 (en) * 2001-08-06 2003-07-10 Degussa Ag, Organosilicon compounds
US20060128870A1 (en) * 2004-12-10 2006-06-15 Marx Ryan E Filled polymer composites
US20070203274A1 (en) * 2006-02-24 2007-08-30 Karsten Korth Rubber mixtures
US20080314490A1 (en) * 2006-03-03 2008-12-25 The Yokohama Rubber Co., Ltd. Low Permeability Rubber Laminate and Pneumatic Tire Using the Same
US20090065118A1 (en) * 2006-04-18 2009-03-12 The Yokohama Rubber Co., Ltd. Low-permeability rubber laminate and pneumatic tire using the same
WO2007123220A1 (en) * 2006-04-18 2007-11-01 The Yokohama Rubber Co., Ltd. Layered low-permeability rubber product and pneumatic tire comprising the same
WO2008009514A1 (en) * 2006-07-17 2008-01-24 Evonik Degussa Gmbh Mixtures of silicon-containing coupling reagents
US20110034584A1 (en) * 2006-07-17 2011-02-10 Philipp Albert Mixtures of silicon-containing coupling reagents

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TOTAL - Blow Moulding. Retrieved on 11/13/2012. http://www.totalrefiningchemicals.com/EN/aboutus/understand_petrochemicals/processing_techniques/Pages/Blow_Moulding.aspx *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130123428A1 (en) * 2008-08-25 2013-05-16 The Yokohama Rubber Col, Ltd. Method for Preparing a Modified Ethylene-Vinyl Alcohol Copolymer
US8969475B2 (en) * 2008-08-25 2015-03-03 The Yokohama Rubber Co., Ltd. Method for preparing a modified ethylene-vinyl alcohol copolymer
US20160039247A1 (en) * 2013-03-15 2016-02-11 Bridgestone Americas Tire Operations, Llc Light-Weight Inner Tube And Related Methods
US10792956B2 (en) * 2013-03-15 2020-10-06 Bridgestone Americas Tire Operations, Llc Light-weight inner tube and related methods
US11667154B2 (en) 2013-03-15 2023-06-06 Bridgestone Americas Tire Operations, Llc Light-weight inner tube and related methods
US20150165586A1 (en) * 2013-12-17 2015-06-18 Fujibo Holdings, Inc. Resin Lapping Plate and Lapping Method Using the Same
US9370853B2 (en) * 2013-12-17 2016-06-21 Fujibo Holdings, Inc. Resin lapping plate and lapping method using the same
US20220186858A1 (en) * 2019-03-11 2022-06-16 Contitech Techno-Chemie Gmbh Coolant hose

Also Published As

Publication number Publication date
JP4488097B2 (en) 2010-06-23
KR20100024343A (en) 2010-03-05
US20130123428A1 (en) 2013-05-16
US8969475B2 (en) 2015-03-03
CN101659724A (en) 2010-03-03
ATE521644T1 (en) 2011-09-15
CN101659724B (en) 2013-08-07
JP2010047733A (en) 2010-03-04
EP2159234A1 (en) 2010-03-03
EP2159234B1 (en) 2011-08-24

Similar Documents

Publication Publication Date Title
US8969475B2 (en) Method for preparing a modified ethylene-vinyl alcohol copolymer
US8616255B2 (en) Polymer laminate and pneumatic tire using the same as inner liner
JP5644332B2 (en) Method for producing thermoplastic elastomer composition
US8835557B2 (en) Polymer composition for inner liner and pneumatic tire using the same
US7600546B2 (en) Pneumatic tire comprising an innerliner
KR101215755B1 (en) Multilayer body, method for producing the same, and pneumatic tire
JP5039332B2 (en) Inner liner for pneumatic tire and pneumatic tire provided with the same
JP2004176048A (en) Inner liner for use in pneumatic tire, and pneumatic tire
WO2006100872A1 (en) Heavy-load tire
JP2006167919A (en) Laminate, its manufacturing method and tire using the laminate
WO2009116308A1 (en) Laminate and pneumatic tire using the laminate
JP2009274680A (en) Heavy duty tire
US20140020807A1 (en) Radial tire for heavy load
JP5440249B2 (en) Modified ethylene-vinyl alcohol copolymer, process for producing the same, and gas barrier resin composition
JP4468073B2 (en) Emergency pneumatic tires
JP5206224B2 (en) Pneumatic tire
JP2007008186A (en) Inner liner for pneumatic tire, and pneumatic tire
JP6136240B2 (en) Method for producing a film for a pneumatic tire member comprising a thermoplastic resin composition
CN112739777A (en) Inner liner for tire and pneumatic tire

Legal Events

Date Code Title Description
AS Assignment

Owner name: THE YOKOHAMA RUBBER CO., LTD.,JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MOROOKA, NAOYUKI;REEL/FRAME:022832/0713

Effective date: 20090603

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION